Sulfurized dyes and process of making same.



UNITED STATES PATENT oFFIoE.

HEINRICH HEIMANN, 0F DESSAU, GERMANY, ASSIGNOR T0 ACTIEN GESELLSCHAFT FfiR ANILIN FABBIKALEION, OF BERLIN, GERMANY.

SULFURI ZED DYES AND PROCESS OF MAKING SAME.

No Drawing.

Specification of Letters Patent.

Patented May 26, 1914.

Application filed October 16, 1912. Serial No. 726,122.

- Dessau, Germany, my post-oifice address being Friedrich-Schneider strass'e 63, .Dessau, Germany, have invented new and useful Improvements in Sulfurized Dyes and Processes of Making Same, of which the following is a specification.

In my co-pending. application Serial No. 726,121 I describe and claim generally new sulfurized dyes fast to washing and to hlorin which may be obtained by acting with a sulfurizing agent upon a 4-hydroxydiarylamin in which only the 4-hydroxyaryl group is capable of assuming the paraquinoid form. Now in my present application I claim a special class ofthese dyestuffswhich derive from such 4-hydroxy-diarylamins in which the 4-position is occupied by an alkyl group or from their derivatives in which the two benzene nuclei contain further univalent substituents, such as a halogen, an alkyl' or alkoxy group,- roup,-

the corresponding derivatives of .thiodi-' phenylamin; thus for instance instead of 4 hydroxy 4' methyldiphenylamin I can also employ the 4:ox y-4'-methylthiodiphenylamin.

The following examples may serve to illustratemy invention, the parts being by weight: I

1. 60 parts of sulfur are dissolved'in 180 parts by volume of a sodium sulfid solution tion are introduced 30 parts of 4-hydroxy-.

containing 50% ofNa S.9H,O into this solured-brown tints with a yellow cast; they possess a very good fastness to washing and remarkable fastness to chlorin.

2. 100 parts of 4-hydroxy-eU-methyldiphenylamin and 100 parts of sulfur are heated during 2-4 hours to about 180 to 200 ,C.,

' whereupon the mass is brought to a temperature of 200-220 C. and this temperature is maintained during 7 10 hours; The new dye .thus obtained may be isolated in the usual manner; it dyes cotton red-brown tints of a very good fastness to washing and of a remarkable fastness to chlorin.

It is obvious to those skilled in the art that my present invention is not limited to the foregoing examples or to the details given therein. of the 4-hydroXy-4-methyldiphenylamin a chloro derivative or an alkyl derivative thereof may be used; instead of apolysulfid or of sulfur alone sulfur in combination with a condensing agent may be employed.

The new dyes as obtained above represent in the dry state when pulverized, generally speaking, dark brown powders which are practically insoluble in alcohol, glacial acetic acid and benzene and which are very ditlieutly soluble in nitro-benzene, anilin, pyridin and chloro derivatives of benzene, these solutions being, generally speaking, yellow-brown to red-brown colored. They dissolve in concentrated sulfuric acid, generally speaking, to'a blue solution and in 25% fuming sulfuric acid, generally speaking, to a violet solution, these solutions remain unaltered on the addition of boric acid, but are 'gradually decolorized by the addition of aluminium powder.

The new dyes produce on cotton from a dye-bath containing an alkali sulfid, gener ally speaking, red-brown or brown-red tints, which are very fast to washing and re Thus for instance instead markably fast to chlorin; the new dyes are also capable ,of being dyed from a hydrosul-.

fite v-at giving, generally speaking, brownred tints.

Having now described my invention and the manner in which it may be carried out, what I claim is,-

dyes fast to washing and to chlorin by actingwith a sulfurizing agent upon a d-hydroxy-l-alkyldiphenylamin containing no sulfonic group and having the following nucleus:

l l l l in which diagram'R means an alkyl grou 2. The manufacture of new sulfurized dyes fast to washing and to chlorin by acting with a polysulfid upon a 4-hydroxy-4- alkyldiphenylamin containing no sulfonic group and having the following nucleus:

II II l I I I l in which diagram R means an alkyl group. 3. The manufacture of new sulfurized dyes fast to washing and to chlorin by act- 3 ing with a polysulfid in the presence of a substance being a liquid at the temperatures prevailing during the reaction upon a 4- hydroxy -a-alkyldiphenylamin containing no sulfonic group and having the following nucleus:

I l l -l r in which. diagram R means an alkyl group.

4. The manufacture of new sulfurized dyes fast to washing and to chlorin by acting with a sulfurizing agent upon 4-hydroxy- 4-methyldiphenylamin.

5. The manufacture of a new sulfurized dye fast to washing and to chlorin by acting avith a polysulfid upon4 hydroxy-4J-methylin which diagram R means all alkyl group,

.1 these new dyes representing in the dry state when pulverized dark brown powders which are practically insoluble in alcohol. glacial acetic acid and benzene and which are very difficultly soluble in nitrobe-nzene, anilin, pyridin and chloro derivatives of benzene, these solutions being, generally speaking, yellow-brown to red-brown colored, which new dyes dissolve in concentrated sulfuric acid, generallyv speaking, to a blue solution and in 25% fuming sulfuric acid, generally speaking, to a violet solution, which solutions on the addition of boric acid remain unaltered but are gradually decolorized by the addition of aluminium powder, and

which new dyes produce on cotton from a dye-bath containing an alkali sulfid, generally speaking, red-brown to brown-red tints which are very fast to washing and remarkably fast to chlorin, and which new dyes are also capable of being dyed from a hydrosulfite vat giving, generally speaking, brown red tints.

8. As new articles of manufacture new sulfurized dyes, very fast to washing and remarkably fast to chlorin', which may be obtained from a thydroxy-l-methyldiphenylamin by the action of a sulfurizing agent, these new dyes representing in the dry state when pulverized dark brown powders which are practically insoluble in alcohol, glacial acetic acid and benzene and which. are very diflicultly soluble in nitrobenzene, anilin, pyridin and chloro derivatives of benzene, these solutions, being, generally speaking, yellowbrown to red-brown colored, which new dyes dissolve in concentrated sulfuric acid, generally speaking, to a blue solution and vin 25% fuming sulfuric acid, generally speaking, to a violet solution, which solutions on the addition of horic acid remain unaltered but are gradually decolorized by the addition of aluminium powder, andwhich new dyes produce on cotton from a dyeba'th containing a-n'alkali sulfid, generally speaking, red-brown to brown-red tints which are very fast to washing and re markably fast to chlorin, and which new dyes are also capable of being dyed from a hydrosulfite vat giving, generally speaking, brown-red tints.

9. As a new article of manufacture the new sulfurized dye, which may be obtained from 4hydroxy-4'-methyldiphenylamin by the action of an alkali polysulfid, this new dye representing in the dry state when pulverized a dark red-brown powder which is practically insoluble in alcohol, glacial acetic acid and benzene and which is very diificultly soluble in nitrobenzene, anilin,

pyridin and chloro derivatives of benzene to a red-brown solution, and which new dye dissolves in concentrated sulfuric acid to a blue solution and in 25% fuming sulfuric acid to a violet solution which solutions on the addition of boric acid remain unaltered but are gradually decolorized by the addition of aluminium powder, and this new dye producing on unmordanted cotton from a dye-hath coi'itaining an alkali sulfid a brmvni In testimony whci'eof I have signed my red tint with a yellow cast which is very name hi this specification in the presence fast to washing and remarkably fast, to i of two subscribing Witnesses chlorin, and which new dye is also capable HEINRICH HEIMANN.

5 of dyeing uninordanted cotton from a hydro- Witnesses:

sulfite vat forming a yellow vat, which gives. RUDOLPH FBICKE,

a brown-red tint with a yellow cast. Denis KRAHL. 

